Improvement of d–d interactions in density functional tight binding for transition metal ions with a ligand field model: assessment of a DFTB3+U model on nickel coordination compounds
Abstract
To improve the description of interactions among the localized d, f electrons in transition metals, we have introduced a ligand-field motivated contribution into the Density Functional Tight Binding (DFTB) model. Referred to as DFTB3+U, the approach treats the d, f electron repulsions with rotationally invariant orbital–orbital interactions and a Hartree–Fock model; this represents a major conceptual improvement over the original DFTB3 approach, which treats the d, f-shell interactions in a highly averaged fashion without orbital level of description. The DFTB3+U approach is tested using a series of nickel compounds that feature Ni(II) and Ni(III) oxidation states. By using parameters developed with the original DFTB3 Hamiltonian and empirical +U parameters (F0/2/4 Slater integrals), we observe that the DFTB3+U model indeed provides substantial improvements over the original DFTB3 model for a number of properties of the nickel compounds, including the population and spin polarization o...f the d-shell, nature of the frontier orbitals, ligand field splitting and the energy different between low and high spin states at OPBE optimized structures. This proof-of-concept study suggests that with self-consistent parameterization of the electronic and +U parameters, the DFTB3+U model can develop into a promising model that can be used to efficiently study reactive events involving transition metals ion condensed phase systems. The methodology can be integrated with other approximate QM methods as well, such as the extended tight binding (xTB) approach.
Source:
Physical Chemistry Chemical Physics, 2020, 22, 46, 27084-27095Publisher:
- American Chemical Society
Funding / projects:
- Serbian–German collaboration project (DAAD) number 451-03-01038/2015-09/7 (to MG and ME).
- Ministry of Education, Science and Technological Development, Republic of Serbia, Grant no. 200168 (University of Belgrade, Faculty of Chemistry) (RS-200168)
- Ministry of Education, Science and Technological Development, Republic of Serbia, Grant no. 200026 (University of Belgrade, Institute of Chemistry, Technology and Metallurgy - IChTM) (RS-200026)
- NIH grant R01-GM106443 (QC) and the Spanish Ministry of Economy and Competitiveness through Grant PGC2018-096955-B-C41 (PGF).
DOI: 10.1039/D0CP04694A
ISSN: 1463-9076
WoS: 000597256600040
Scopus: 2-s2.0-85097578431
Collections
Institution/Community
Hemijski fakultet / Faculty of ChemistryTY - JOUR AU - Stepanović, Stepan AU - Lai, Rui AU - Elstner, Marcus AU - Gruden, Maja AU - Garcia-Fernandez, Pablo AU - Cui, Qiang PY - 2020 UR - https://cherry.chem.bg.ac.rs/handle/123456789/4299 AB - To improve the description of interactions among the localized d, f electrons in transition metals, we have introduced a ligand-field motivated contribution into the Density Functional Tight Binding (DFTB) model. Referred to as DFTB3+U, the approach treats the d, f electron repulsions with rotationally invariant orbital–orbital interactions and a Hartree–Fock model; this represents a major conceptual improvement over the original DFTB3 approach, which treats the d, f-shell interactions in a highly averaged fashion without orbital level of description. The DFTB3+U approach is tested using a series of nickel compounds that feature Ni(II) and Ni(III) oxidation states. By using parameters developed with the original DFTB3 Hamiltonian and empirical +U parameters (F0/2/4 Slater integrals), we observe that the DFTB3+U model indeed provides substantial improvements over the original DFTB3 model for a number of properties of the nickel compounds, including the population and spin polarization of the d-shell, nature of the frontier orbitals, ligand field splitting and the energy different between low and high spin states at OPBE optimized structures. This proof-of-concept study suggests that with self-consistent parameterization of the electronic and +U parameters, the DFTB3+U model can develop into a promising model that can be used to efficiently study reactive events involving transition metals ion condensed phase systems. The methodology can be integrated with other approximate QM methods as well, such as the extended tight binding (xTB) approach. PB - American Chemical Society T2 - Physical Chemistry Chemical Physics T2 - Physical Chemistry Chemical PhysicsPhys. Chem. Chem. Phys. T1 - Improvement of d–d interactions in density functional tight binding for transition metal ions with a ligand field model: assessment of a DFTB3+U model on nickel coordination compounds VL - 22 IS - 46 SP - 27084 EP - 27095 DO - 10.1039/D0CP04694A ER -
@article{ author = "Stepanović, Stepan and Lai, Rui and Elstner, Marcus and Gruden, Maja and Garcia-Fernandez, Pablo and Cui, Qiang", year = "2020", abstract = "To improve the description of interactions among the localized d, f electrons in transition metals, we have introduced a ligand-field motivated contribution into the Density Functional Tight Binding (DFTB) model. Referred to as DFTB3+U, the approach treats the d, f electron repulsions with rotationally invariant orbital–orbital interactions and a Hartree–Fock model; this represents a major conceptual improvement over the original DFTB3 approach, which treats the d, f-shell interactions in a highly averaged fashion without orbital level of description. The DFTB3+U approach is tested using a series of nickel compounds that feature Ni(II) and Ni(III) oxidation states. By using parameters developed with the original DFTB3 Hamiltonian and empirical +U parameters (F0/2/4 Slater integrals), we observe that the DFTB3+U model indeed provides substantial improvements over the original DFTB3 model for a number of properties of the nickel compounds, including the population and spin polarization of the d-shell, nature of the frontier orbitals, ligand field splitting and the energy different between low and high spin states at OPBE optimized structures. This proof-of-concept study suggests that with self-consistent parameterization of the electronic and +U parameters, the DFTB3+U model can develop into a promising model that can be used to efficiently study reactive events involving transition metals ion condensed phase systems. The methodology can be integrated with other approximate QM methods as well, such as the extended tight binding (xTB) approach.", publisher = "American Chemical Society", journal = "Physical Chemistry Chemical Physics, Physical Chemistry Chemical PhysicsPhys. Chem. Chem. Phys.", title = "Improvement of d–d interactions in density functional tight binding for transition metal ions with a ligand field model: assessment of a DFTB3+U model on nickel coordination compounds", volume = "22", number = "46", pages = "27084-27095", doi = "10.1039/D0CP04694A" }
Stepanović, S., Lai, R., Elstner, M., Gruden, M., Garcia-Fernandez, P.,& Cui, Q.. (2020). Improvement of d–d interactions in density functional tight binding for transition metal ions with a ligand field model: assessment of a DFTB3+U model on nickel coordination compounds. in Physical Chemistry Chemical Physics American Chemical Society., 22(46), 27084-27095. https://doi.org/10.1039/D0CP04694A
Stepanović S, Lai R, Elstner M, Gruden M, Garcia-Fernandez P, Cui Q. Improvement of d–d interactions in density functional tight binding for transition metal ions with a ligand field model: assessment of a DFTB3+U model on nickel coordination compounds. in Physical Chemistry Chemical Physics. 2020;22(46):27084-27095. doi:10.1039/D0CP04694A .
Stepanović, Stepan, Lai, Rui, Elstner, Marcus, Gruden, Maja, Garcia-Fernandez, Pablo, Cui, Qiang, "Improvement of d–d interactions in density functional tight binding for transition metal ions with a ligand field model: assessment of a DFTB3+U model on nickel coordination compounds" in Physical Chemistry Chemical Physics, 22, no. 46 (2020):27084-27095, https://doi.org/10.1039/D0CP04694A . .